Nucleophilic character of acyl radicals. Absolute rate constant for the acylation of protonated benzothiazole by pivaloyl radical

Abstract

The absolute rate consta-t for the addition of pivaloyl radical to protonated benzothiazole is determined by evaluating the ratio of decarbonylation and aromatic attack. The high rate constant (7.1 × 10⁵ l mol^–1 s^–1 at 5 °C) is discussed in terms of polar effects and a divergence from the classical reactivity: selectivity relationship is suggeste